Detergent and wetting compositions



NlTED STATES I 2,388,027 nr'rmcsm AND warms coMrosmoNs Clyde 0. Henke,Wilmington, Del., assignor to E. I. I du Pont de Nemours d: Company,Wilmington,

rric

Del., a corporation of Delaware No Drawing. Application April 1, 1942,

Serial No. 487,277

Claims. (Cl. 252-161) This invention relates to surface activecompositions comprising purified aliphatic and/or cycloaliphaticsulfonic acids or their salts. More particularly it relates to surfaceactive compositions comprising a mixture of saturated hydrocarbon sodiumsulfonates containing from '12 to 20 carbon atoms, a lower aliphaticalcohol, a

higher aliphatic alcohol, and a water-soluble alkali metal salt. Theinvention also relates to the preparation and use of such compositions.

This application is a continuation-in-part of copending application,Serial No. 352,797, filed August 15, 1940 (and issued December 28. 1943,as Patent No. 2,337,552), which application is directed to thepreparation and purification of the surface active compounds used in thenovel compositions of this invention.

When a saturated hydrocarbon or a mixture of such hydrocarbons isreacted with a mixture of sulfur dioxide and chlorine at a temperaturebelow the decomposition point of the formed organic sulfonyl chloridesunder the influence of actinic light in the above-identified manner, arather complex mixture of products is formed which contains hydrocarbonmonosulfonyl chlorides, chlorhydrocarbon monosulfonyl chlorides,chlor-hydrocarbon polysulfonyl chlorides, hydrocarbon polysulfonylchlorides, chloro-hydrocarbons and unreacted hydrocarbons. Similarresults are obtained with hydrocarbon derivatives. The proportion ofproducts in the mixture can be varied somewhat by varying theproportions of sulfur dioxide to chlorine, the rate of flow, theintensity of the actinic light used to accelerate the reaction,pressure, and temperature conditions. If a large proportion ofhydrocarbon is present or only a portion of the available hydrocarbon isreacted a large proportion of hydrocarbon monosulfonyl chlorides isformed. Some substitution, however, takes place whereby chlorhydrocarbonmonosulfonyl chlorides are formed.

In the case where the saturated open chain hydrocarbons and derivativesthereof, e. g. nongaseous n-alkanes, isoalkanes, chloroalkanes andmineral oil fractions free from aromatic and um saturated constituentsare used as initial reactants, the mixtures are usually complex sincethe sulfonyl chloride groups do not enter the same position in eachmolecule. Hence, the resulting alkali metal salts are quite complex whenthe entir fraction or a portion thereof which consists essentially ofhydrocarbon sulfonyl chlorides is used for the hydrolysis andneutralization of such chlorides.

An object of this invention is to provide new surface activecompositions. A further object is to provide such compositions havingimproved deterging and wetting-out properties. Another object isto'provide such compositions having improved sudsing properties. Afurther object is to provide compositions having good sudsing anddeterging properties containing surface active agents obtained frompurified mixtures of higher aliphatic and/or cycloaliphatic sulfonylhalides. especially chlorides. Another object is to prepare suchcompositions by utilizing economical and readily available materials andapparatus, Still other objects will be apparent from a consideration ofthe hereinafter described invention.

The above objects are accomplished by removing the unsulfonatedhydrocarbon, particularly liquid hydrocarbon or oil from an aqueousmixture of water-soluble higher aliphatic or cycloaliphatic sulfonatesfrom crude reaction mixtures by a liquid phase extraction with a highboilin hydrocarbon compound, admixing the surface active .compounds inthe aqueous portion with from'l% to 15% by weight of a water immiscibleor insoluble alcohol and 1% to 20% of a water miscible or solublealcohol.

In one important aspect the invention involves removing the unsulfonatedhydrocarbon, particularly liquid hydrocarbon or oil from an aqueoussolution of water-soluble higher aliphatic or cycloaliphatic sulfonatesobtained by a conversion of the corresponding sulfonyl halides by aliquid phase extraction with a high boiling hydrocarbon. The surfaceactive compounds in the aqueous phase are admixed with theabove-described amounts of a water-immiscible alcohol and awater-miscible alcohol.

In a practical embodiment a high boiling liquid or normally solidhydrocarbon or a derivative thereof is used as the extracting agent. Theextraction is carried out in the liquid state. The bulk of thehydrocarbon material is removed while in the molten state, the aqueouslayer is then cooled and the hydrocarbon portion which settles out isremoved and the filtrate is concentrated. The surface active compoundsare admixed with a water-immiscible and water-miscible alcohol in theabove amounts.

The compositions may in addition to said alcohols contain from 25% to ofWater. All amounts are by weight and based upon the surface activecompounds.

The invention may be used with a wide variety of sulfonates as will bedescribed hereinafter. It is particularly adapted to the use of thesurface 66 active. compounds obtained by the purification and separationof sulfonates containing an all- I phatic hydrocarbon nuclei of at least5 carbon 1. minutes.

atoms or a cycloaliph'atic hydrocarbon nuclei of I at least 6hydrocarbons from mixtures containing hydrocarbons or hydrocarbonderivatives containing nuclei of the same number of carbon atoms incompositions of the above-described character.

The invention is further illustrated but is not intended to be limitedby the following examples wherein the parts stated are by weight.

Example I The sodium salts of hexadecane sulfonic acids are prepared bypassing a gaseous mixture of 89 parts of sulfur dioxide and 70 parts ofchlorine into 300 parts of hexadecane over a period of, 30

sodium sulfonates by hydrolyzing-with 240 parts of hot 30% sodiumhydroxide. To the resulting product are added 300 parts of moltenrefined paraflin wax, having a melting point of 50 C. (122 F.), 1300parts of water, and 101 parts of ethyl alcohol. The mixture is heatedand stirred and let stand. The molten paraiiin and unsuiaseaoavone-hundredths of its weight of ethyl alcohol,

heated to 60-65 C.. and allowed to stand. The

major portion of unsulfonated oil separates as a top layer. The loweraqueous layer is withdrawn and analyzes 12.3% aliphatic sodium sulfonateand 1.02% unsulfonated oil.

Fifteen hundred parts of this solution is stirred with 75 parts ofparaffin wax melting at 130 1". (54 C.) and 75 parts of isopropylalcohol at 60-65 C. for minutes. slowly to 17 C. A solid cake of waxseparates on top and is removed. The remaining crystallized wax isfiltered off. The resulting iiltr'ate analyzes 12.5% aliphatic sodiumsulfonateand 0.23% unsulfonated oils.

Eleven hundred and eighty-eight parts of the filtrate is heated to 95 C.with 290 parts of sodium chloride and 83. parts of water. The mixture ispoured into a separatory funnel. A separation into layers takes placequickly. a concentrated sodium chloride solution forming the lower layerand a concentrated aliphatic sodium sulfonate solution forming the upperlayer. The

' lower layer is drawn 01! and discarded. The

fonated oils separate as a top layer. The lower aqueous layer, which is1512 parts by weight shows on analysis a hexadecane sodium sulfonatecontent of 11.0% and an unsulfonated oil content of 0.37%. A wettingtest by the Braves- Clarkson skein sinking method shows sinking in 25seconds at 77 F. at a concentration of 0.68 g. hexadecane sodiumsulfonate per liter.

Naphthalene may be substituted for fin wax with similar results.

Example II A crude aqueous solution of the hexadecane sodium sulfonatesprepared as in Example I of 692 parts by weight isdiluted with. 1284parts of water and 100 parts of ethyl alcohol and the parafheated. to 60C. On standing'the major portion of the unreacted hexadecane separatesas a top layer. The lower aqueous layer is withdrawn and stirred with300 parts of paraflln at IO-80 C. for one hour. The mixture is'pouredinto a separatory funnel and the major proportion of the pa'raillnseparates as a molten upper.

layer. The lower aqueous layer is withdrawn and cooled. Solid parailincrystallizes out from the aqueous solution and is filtered oil at 22 C.The aqueous filtrate analyzes 12.6% hexadecane sodium sulfonate and0.37% unsulfonated oil. Theproduct has wettingproperties similar to thatof Example I.

Example In A Pennsylvania base mineral oil is purified by suitable meansso that it is substantially free from aromatic and olefinic constituentsand has the following characteristics: A distillation range of 267 C. to310 0.; a Baybolt Universal viscosity at 100 F. of 37 seconds; arefractive index at- 20 C. of 1.444; a specific gravity at 15.5 C.compared to water at 15.5 6.0! 0.804. This oil is treated with a gaseousmixture of sulfur dioxide and chlorine in a molar ratio of 1.4 to 1.0 atabout 30 C. in the presence of light having a radiation range of 4000 Ato 5800 A until the specific gravity at 30 is 0.940. The resultingaliphatic upper layer of concentrate is 443 parts by weight. To theupper layer is added 22 parts by weight of isopropylalcohol and themixture is heated to- 70. A further separation of sodium chloridesolution andsodium chloride occurs as a lower layer which is drawn off.The upper layer of 384 parts by weight is diluted with 34 parts of waterto give a clear stable solution. This solution analyzes 31.7% aliphaticsodium sulfonates and a wetting test shows that 2.1 g. of the solutionper liter gives sinking in 25 seconds by the Dr'aves- Clarksonskein-sinking method. To 200 parts of the above solution are added 4parts of n-octyl alcohol to form a clear solution. This product whentested for wetting eiiloiency as above shows sinking in 25 seconds at aconcentration of 1.8 g. per liter. a Y

' Naphthalene may be substituted for the paraffin wax with similarresults.

Example IV Fifteen hundred parts of a sodium alkyl sulfonate solutionanalyzing 10.3% active ingredient prepared as in the first paragraph of.Example III Example III.

weight. To this was added 18 parts of water and a clear solution wasobtained. The product gave wetting by the Draves-Clarkson skein-sinkingmethod of 1.89 8. per liter at 25 C. The product likewise has excellentsudsing and detergent properties. If desired, the solution of so-v diumalkyl sulfonates may be extracted with parailln before the salting outstapes disclosed in Example 1! A.gaseous mixture of 902 parts by weight0! sulfur dioxide and 297 parts by weight of chlorine The mixture iscooled were passed at a uniform rate for four hours through 200 parts byweight of menthane contained in a flask which was illuminated by a 80-watt incandescent light. Heat was evolved during the reaction. Thetemperature was maintained at 40 C. by means of a water bath. At the endof four hours the menthane had gained 201 parts byweight. The productformed at this stage apparently contained menthane sulfonyl' chlorides,chlormenthane sulfonyl chlorides and small amounts of chlormenthane. Thereaction product was then added to 500 parts of 30% sodium hydroxidesolution. The temperature during neutralization was maintained at 90 to95 0. About 883 parts of product were obtained. The product was dilutedwith 237 parts of water. An insoluble oil layer separated and wasremoved.

To 900 parts of the solution so obtained were added 75 parts of aparafiln wax melting at C. and the mixture was heated'to 65 C. andstirred for 30 minutes. The mixture was poured into a separatory funneland allowed to stand whereupon a layer of molten parailln separated atthe top. The lower aqueous layer was withdrawn and cooled to 20 C. Solidparaffin precipitated out. This was removed by filtration and clear paleyellow aqueous solution was obtained. This solution showed high wettingpower when dissolved in 52 Tw. caustic soda solution.

The extraction procedure may be modified in thalene, etc., alkanes, e.g., eicosane, heneicosane, tricosane, hentriacontane, pentatriacontaneand hexacontane, etc., and their halogen derivatives;

the normally solid high molecular weight monohydric alcohols, e. g.dodecyl, tetradecyl, hexadecyl and octadecyl and their fatty acidesters,

. preceding examples.

a number of ways without departing from the scope of the invention.Thus, the extraction of the unsulfonated oil may be made at anyconvenient temperature from the melting point of the hydrocarbon orderivative or lower to the boiling point of the solution. Various watermiscible agents such as methyl, ethyl, propyl and isopropyl alcohols,acetone, etc. may be added to the solution to lower the amount ofparaffin wax emulsified in the solution if desired.

The temperature to which the solution may be cooled before filtering offthe separated or crystallized hydrocarbon or derivative may be variedbut in general a temperature is selected slightly above that at whichthe aliphatic sulfonates would tend to separate with the hydrocarbon orderivative. The extraction is generally carried out at atmosphericpressure; however, higher pressures may be resorted to if desired.

While each of the working examples is directed to the use of paraffinwax and more particularly to the lower melting parafiln waxes, theextraction procedure is not limited to the use of this narrow class ofmaterials. Various other types of paraflln waxes and petroleumhydrocarbon of the materials disclosed herein with similar I waxes ingeneral maybe substituted with similar results. Suitable other waxesinclude match wax, scale wax, hard and soft paraflln wax, higher meltingparaffin .waxes, micro-crystalline paraflln waxes, petrolatum waxes,mixtures of any or all of the above, etc.

Nor is the extraction feature limited to the use of hydrocarbon waxesfor any hydrocarbon or relatively inert derivative which is solid atabout room temperature, i. e. 20 C. and which melts at a more elevatedtemperature, preferably between 30 and 80 C. and which is capable offorming a solution with the unsulfonated oil. ditional materials includehexachloro ethane, aromatic hydrocarbons, e. g. naphthalene, methylanthracene, octadecylbenzene, tetramethyl benzene, acenaphthene, etc.,substituted aromatic hydrocarbons such as p-dichlorobenzene,tetrachlorobenzene, Z-chloronaphthalene, dichloronaph- Suitable ade. g.the acetates, propionates, butyrates, stearates. palmitates, etc.Mixtures of each of the above may also be used.

The water-soluble sulfonates treated are not limited to the sodiumsulfonates set forth in the On the contrary, a wide variety or otherwater-soluble sulfonates may be purified. In addition to alkali metalsalts, including lithium, sodium, potassium, ammonium, calcium,magnesium andother salts, the corresponding free acids may be similarlypurified.

While the preferred extracting agents are normally solid at roomtemperature, it is possible to use the higher molecular weight petroleumoils such as refined lubricating oils of an average molecular weight ofat least 16 carbon atoms. The normally solid alkanes and paraffin waxesand mixtures thereof have a number of distinct advantages in that theyare readily available commercially, low in cost and their use does notintroduce any deleterious material into the final product.

The salting out step may be practiced at various temperatures from roomtemperature to the boiling point of the solution. In general, the higherthe temperature the higher is the concentration of the aliphaticsulfonate solution obtained. A great many electrolytes other than thoselisted in the specific examples may be substituted therefor or used inconjunction with any results. The types of electrolytes useful areexceedingly diverse in character. Representative materials includealkali metal, especially sodium and potassium and ammonium hydroxides,halides, carbonates, nitrates, borates, phosphates, sulfates, formates,acetates, malates, citrates, tartrates'and benzoates. Specific saltsfalling within certain of the above categories include sodium andpotassium chloride, bromide, iodide, metaborate, phosphate (monoanddiand tri-basic), sulfate, ammonium chloride, zinc chloride, sulfuricacids, hydrochloric acid, etc. In general, electrolyte solutionscontaining at least 20% weight are effective, however, lowerconcentrations can be used. The particular concentration and dodecyl, or."Lo'rol" which is a mixture of higher molecular weight alcohols,terpineol, pine oil. terpenes, terpene alcohols, ammonium sulfama'te.polyvinyl alcohols. etc. may be used to confer various properties on thestandardized product.

The aliphatic and cycloaliphatic sulfonate mixtures purified are notlimited to those set forth in the specific examples. On the contrary,any

of ,thc sulfonates obtained by conversion of normally liquid to solidaliphatic or cycloaliphatic hydrocarbons into sulfonyl chlorides and.hy-

drolysis and neutralization maybe substituted and processed in a similarmanner. Suitable sulfonates are disclosed in U. S. Patents 2,174,505,

' 2,174,506, 2,174,507, 2,174,508, 2,174,509 2,197,800, and 2,263,312.The sulfonates which may be purified are not limited to those obtainedfrom a reaction with admixed sulfur dioxide and a halogenor sulfurylhalides and subsequent hydrolysis and neutralization as described above,but may be applied to the sulfonate products obtained by chlorinating'higher'alkanes, mineral oils, etc.,

' then reacting the resulting chlorinated products with thiourea to givethe isqhiourea derivative, oxidizing the resulting products withchlorine water and hydrolyzing and/or neutralizing the resultingsulfonyl chlorides. The last-mentioned processes are set forth inn. 8.Patents 2,142,934,

2,148,744, 2,147,346, and 2,174,856.

Furthermore, solutions of sulfonates obtained in other ways such as theoxidation ofsulfides or mercaptans, the action of sulfites onhalogenated hydrocarbons, the sulfonation of hydrocarbons or theirderivatives with sulfonatim agents vmay be purified by this method. 7 Ii The water-soluble compositions produced according to thisinventionhave considerable surface-activity and other valuableproperties, and

in providing improved ceramic assistants and processes to improve thesetting of cement. They may also be useful in storage batteries and drycells.'- Other uses for these products or their derivatives are asfungicides, accelerators, delusterants, extreme pressure lubricants,moth proofing agents, antiseptics, fire-proofing agents, mildewpreventers, penetrating agents, anti-fiexing agents, tanning agents,lathering agents, dust collecting agents, antioxidants. colorstabilizers in gasoline, etc.

The surface activity of some of the herein described compositions may bemodified or in somecases enhanced by the-addition'of other surfaceactiveagents, e. g. alkylated naphthalene sulionic phosphonium compounds,aswell as numerous may be used as mercerizing assistants, corrosioninhibitors, gum solvents for gasoline, extractants 1 for the refining ofgasoline, pour point depressants, insecticides, fiy spray ingredients,weed kil1ers,soil fuinigants, cotton immunization chemicals,anti-shrinking agents for wool, foaming agents. mold inhibitors,lubricants for steel drawing andmetal working, crease-proofing agents,viscose modifiers, pharmaceuticals, detergents, wetting agents,rewet'ting agents, for improving textile treating processes,. includingwool scouring, carbonizing, fulling, sizing, desizing, bleaching,mordanting, lime soap dispersing, improvement of absorption,delustering, degumming, kier boiling," felting, oiling. lubricating,resisting cotton in an acid bath; dyeing, printing, stripping,-

creping, scouring viscose rayon, etc'. They may also be useful inimproving dye compositions,-

printing paste, the preparationsof lakes, the preparation of inorganicplgmentsand household dye preparations. They may also be useful inimproving processes of dyeing leather and textiles including dyeing withdeveloped dyes, dyeing in neutral, acid or alkaline dye baths; dyeing ofanimal fibers with vat dyes. etc.

They may also be useful in treating oil wells I and to improve floodingoil bearing sands. They may also be used to improve radiator cleaningcompositions, cleansing compositions as household detergentcompositions, shampoos, dentii'rices, washing of paper mill felts, etc.They may also be used to-improve fat liquoring and leather treatmentprocesses as well as for fat splitting agents. They may also be usefulin improving the preservation of green fodder. They may also be usefulayers from surfaces and in metal cleaning. They may also be used toimprove flotation processes of ores, pigments, coal, etc. They may alsobe useful in breaking petroleum emulsions or in different concentrationsas emulsifying agents. They may also be useful in improving foodpreparations. They may be useful in improving the cooking of-wood pulp.Theymay also be usefulother soap substitutes.

Theinvention has particular utility in purifying the sodium andpotassium sulfonates obtained from the alkane monoand poly-sulfonylchlo-' rides and chloroalkane mono.. and poly-sulfonyl I chlorideshaving at least 12 carbon atoms from mixtures containing them andnormally liquid or solid hydrocarbons. The surface activity. detergingand wetting properties of these products are enhanced quite materially.a Furthermore, the

surface activity per unit of weight is substantheincreased contiallyincreased by virtue of centration of the product.

The proces of extraction of the unsulfonated oil from the aliphaticsodium sulfonate solutions is a very appreciable improvement over theordinary methods of extraction with volatile solvents. When solventssuch as pe roleum ether,

ethylene, etc. are used, very stable emulsions are formed. The emulsionmay be so permanent that a clear solution of the solvent in thealiphatic sulfonate solution is formed. It is dimcult to break theseemulsions. When the solution is carbon tetrachloride, benzene, ether-trichlor .heated to drive on the emulsified solvent, the unreacted oildissolved by the solvent is left in solution. However-{when paramn wax,for example, is iised as the solvent, the solubility in the aqueousaliphatic sulfonate is more limited.

' Further, when the solution is cooled so that the small amount ofemulsified paraiiln will crystallize, the unreacted oil stays in thesolid parafiln rather than in the solution and'is filtered off.

The salting out step of the process is advantageous in that it permitsan easy way to obtain concentrated solutions. necessary to evaporate thewater from the solution. This evaporation is accompanied by excessivefoaming and some darkening of color of the solution.

in imp oving the removal of fibrous r As many apparently widelydifferent embodi- I ments of this invention may be made withoutdeparting from the spirit and scope thereof, it is to be understood thatI do not intend to limit my self to the specific embodiments herein,except as defined by the appended cl I In the claims below, theexpression "non-aromatic hydrocarbon is to be understood as a simplifiedgeneric phrase defining a hydrocarbon selected from the group consistingof aliphatic and cycloaliphatic hydrocarbons.

Otherwise it would be salts thereof, having at least carbon atoms andbeing the residue left after extraction in the liquid phase with ahydrocarbon which is solid at C. of the aqueous mass obtained byhydrolysis of a crude reaction mass comprising sulionylchloridederivatives of non-aromatic hydrocarbons having at least 5 carbon atomsin admixture with unreacted hydrocarbons oi the same group.

2. A composition of matter having detergent and wetting propertiescomprising 1 to 15% by weight of a water-immiscible alcohol, 1-20% byweight of a water-miscible alcohol, the said percentages being based onthe weight of the salt hereinafter defined; and a water-soluble salt ofa saturated aliphatic hydrocarbon sulfonic acid, having at least 12carbon atoms and being the residue left after extraction in th liquidphase,

with a hydrocarbon having a melting point between and 80 C.,'oi theaqueous mass obtained by hydrolyzing a crude reaction product comprisingsulfonyl-chloride derivatives of a saturated aliphatic hydrocarbonhaving at least 12 carbon atoms in admixture with some of the unreactedhydrocarbon.

3. The composition or matter of claim 2, in which the salt is an alkalimetal salt.

4. A composition of matter having detergent and wetting propertiescomprising 1-15% by weight of awater-immiscible alcohol, 1-20% by weightoi a water-miscible alcohol, the said percentages being based on theweight of the salt mixture hereinafter defined, and a water-solublemixture of primary and secondary alkane and chloro-alkane, monoandpolysuli'onic acid alkali metal salts having at least 12 carbon atoms,and being the residue left after extraction in the liquid phase, with ahydrocarbon melting between 30 and C., oi the aqueous mass obtained byhydrolyzing a crude reaction mass comprising the monoandpoly-sulionyl-chloridea corresponding to said sulionates in admixturewith some of the unreacted alkanes having at least 12 carbon atoms.

5. A composition of matter having detergent and wetting propertiescomprising 1-15% by weight of a water-immiscible alcohol, 1-20% byweight of a water-miscible alcohol, the said per centages being based onthe weight of the salt hereinafter defined, and a water-soluble salt oia saturated aliphatic hydrocarbon sulfonic acid having at least 12carbon atoms, and being the residue left after extraction in the liquidphase, with a petroleum hydrocarbon wax, of the aqueous mass obtained byhydrolyzing a crude reaction product comprising sultonyl-chloridederivatives of a saturated aliphatic hydrocarbon having at least 12carbon atoms in admixture with some of the unreacted hydrocarbon.

CLYDE O. HENKE.

